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Abstract:

A fractionation system for a polymerization reactor includes a membrane
separation system designed to separate light components, such as
unreacted monomer and inerts, from diluent. The membrane separation
system may employ one or more membrane modules designed to separate
hydrocarbons based on size, solubility, or combinations thereof. The
fractionation system also may include a heavies fractionation column
designed to separate heavy components, such as unreacted comonomer and
oligomers, from the diluent.

Claims:

1. A fractionation system comprising: a heavies fractionation column
configured to fractionate a first feed stream from an effluent treatment
system to remove heavy components from the first feed stream; and a
membrane separation system configured to separate a second feed stream
from the effluent treatment system into a lights enriched stream
concentrated with light components relative to the second feed stream and
a diluent enriched stream concentrated with diluent relative to the
second feed stream.

2. The fractionation system of claim 1, wherein the membrane separation
system separates the second feed stream based on hydrocarbon solubility.

3. The fractionation system of claim 1, wherein the membrane separation
system separates the second feed stream based on hydrocarbon molecule
size.

4. The fractionation system of claim 1, wherein the membrane separation
system comprises at least two membrane modules.

5. The fractionation system of claim 1, wherein the membrane separation
system comprises at least one membrane configured to allow permeation of
the light components through the membrane.

6. The fractionation system of claim 1, wherein the membrane separation
system comprises at least one membrane configured to allow permeation of
the diluent through the membrane.

7. The fractionation system of claim 1, wherein the fractionation system
does not include a lights fractionation column.

8. The fractionation system of claim 1, wherein the membrane separation
system is an integral component of the heavies fractionation column.

9. A polyolefin production system, comprising: a polymerization reactor
configured to polymerize olefin monomer into polyolefin solids and to
discharge effluent comprising the polyolefin solids, diluent, heavy
components, and light components; an effluent treatment system configured
to treat the effluent to produce a first feed stream, a second feed
stream, and a product stream comprising extracted polyolefin solids; a
heavies fractionation column configured to fractionate the first feed
stream into a first discharge stream concentrated with the heavy
components relative to the first feed stream and a second discharge
stream concentrated with the light components and the diluent relative to
the first feed stream; and a membrane separation system configured to
separate the the second feed stream into a diluent enriched stream
concentrated with the diluent relative to the second feed stream and a
lights enriched stream concentrated with the light components relative to
the second feed stream.

10. The polyolefin production system of claim 9, wherein the
polymerization reactor comprises a loop slurry reactor.

11. The polyolefin production system of claim 9, wherein the diluent
comprises isobutane, and wherein the olefin monomer comprises ethylene.

12. The polyolefin production system of claim 9, wherein the second feed
stream comprises the second discharge stream from the heavies
fractionation column.

13. The polyolefin production system of claim 9, wherein the effluent
treatment system comprises: a separation vessel configured to separate
the effluent into a flash gas stream and a solids discharge; a purge
column configured to separate the solids discharge into the extracted
polyolefin solids and a residual hydrocarbon stream; a separation unit
configured to separate purge gas from the residual hydrocarbon stream to
produce a purge gas recycle stream and the first feed stream; and a
diluent recycle tank configured to separate the flash gas stream into the
second feed stream and a diluent recycle stream.

14. The polyolefin production system of claim 13, wherein at least a
portion of the diluent enriched stream is recycled to the separation
unit.

15. A method for recovering diluent from polymerization reactor effluent,
the method comprising: separating effluent from a polymerization reactor
into extracted polyolefin solids, a first feed stream concentrated with
diluent and heavy components relative to the the effluent, and a second
feed stream concentrated with the diluent and light components relative
to the effluent; fractionating the first feed stream in a heavies
fractionation column to produce a first discharge stream concentrated
with the heavy components relative to the first feed stream and a second
discharge stream concentrated with the diluent relative to the first feed
stream; and separating the second feed stream in a membrane separation
system to produce a diluent enriched stream concentrated with the diluent
relative to the second feed stream and a lights enriched stream
concentrated with the light components relative to the second feed
stream.

16. The method of claim 15, wherein separating the second feed stream in
a membrane separation system comprises directing the second feed stream
through one or more separation membranes that facilitate permeation of
the light components through the separation membranes.

17. The method of claim 15, wherein separating the second feed stream in
a membrane separation system comprises directing the second feed stream
through one or more separation membranes that inhibit passage of the
light components through the separation membranes.

18. The method of claim 15, comprising combining the second discharge
stream from the heavies fractionation column with the second feed stream
upstream of the membrane separation system.

19. The method of claim 15, comprising directing the lights enriched
stream to a flare or to a monomer recovery unit.

20. The method of claim 15, comprising polymerizing olefin monomer in a
loop slurry polymerization reactor in the presence of catalyst suspended
in the diluent to form polyolefin particles and to produce the effluent.

Description:

BACKGROUND

[0001] The present disclosure relates generally to polyolefin production,
and more particularly, to membrane fractionation systems employed in
polyolefin production to facilitate diluent recovery.

[0002] This section is intended to introduce the reader to aspects of art
that may be related to aspects of the present disclosure, which are
described and/or claimed below. This discussion is believed to be helpful
in providing the reader with background information to facilitate a
better understanding of the various aspects of the present disclosure.
Accordingly, it should be understood that these statements are to be read
in this light, and not as admissions of prior art.

[0003] As chemical and petrochemical technologies have advanced, the
products of these technologies have become increasingly prevalent in
society. In particular, as techniques for bonding simple molecular
building blocks into longer chains (or polymers) have advanced, the
polymer products, typically in the form of various plastics, have been
increasingly incorporated into various everyday items. For example,
polyolefin polymers, such as polyethylene, polypropylene, and their
copolymers, are used for retail and pharmaceutical packaging, food and
beverage packaging (such as juice and soda bottles), household containers
(such as pails and boxes), household items (such as appliances,
furniture, carpeting, and toys), automobile components, pipes, conduits,
and various industrial products.

[0004] Specific types of polyolefins, such as high-density polyethylene
(HDPE), have particular applications in the manufacture of blow-molded
and injection-molded goods, such as food and beverage containers, film,
and plastic pipe. Other types of polyolefins, such as low-density
polyethylene (LDPE), linear low-density polyethylene (LLDPE), isotactic
polypropylene (iPP), and syndiotactic polypropylene (sPP) are also suited
for similar applications. The mechanical requirements of the application,
such as tensile strength and density, and/or the chemical requirements,
such thermal stability, molecular weight, and chemical reactivity,
typically determine what polyolefin or type of polyolefin is suitable.

[0005] One benefit of polyolefin construction, as may be deduced from the
list of uses above, is that it is generally non-reactive with goods or
products with which it is in contact. This allows polyolefin products to
be used in residential, commercial, and industrial contexts, including
food and beverage storage and transportation, consumer electronics,
agriculture, shipping, and vehicular construction. The wide variety of
residential, commercial, and industrial uses for polyolefins has
translated into a substantial demand for raw polyolefin, which can be
extruded, injected, blown, or otherwise formed into a final consumable
product or component.

[0006] To satisfy this demand, various processes exist by which olefins
may be polymerized to form polyolefins. Typically, these processes are
performed at or near petrochemical facilities, which have ready access to
the short-chain olefin molecules (monomers and comonomers) such as
ethylene, propylene, butene, pentene, hexene, octene, decene, and other
building blocks of the much longer polyolefin polymers. These monomers
and comonomers may be polymerized in a liquid-phase polymerization
reactor and/or gas-phase polymerization reactor to form polymer
(polyolefin) solid particulates, typically called fluff or granules. The
fluff may possess one or more melt, physical, rheological, and/or
mechanical properties of interest, such as density, melt index (MI), melt
flow rate (MFR), copolymer content, comonomer content, modulus, and
crystallinity. The reaction conditions within the reactor, such as
temperature, pressure, chemical concentrations, polymer production rate,
and so forth, may be selected to achieve the desired fluff properties.

[0007] In addition to the one or more olefin monomers and/or comonomers, a
catalyst for facilitating the polymerization may be added to the reactor.
For example, the catalyst may include particles added to the reactor in a
reactor feed stream to produce catalyst particles suspended in the fluid
medium within the reactor. An example of such a catalyst is a chromium
oxide containing hexavalent chromium on a silica support. Further, a
diluent may be introduced into the reactor. The diluent may be an inert
hydrocarbon, such as isobutane, propane, n-pentane, i-pentane,
neopentane, and n-hexane that is liquid at reaction conditions. Further,
some polymerization processes may not employ a separate diluent, such as
in the case of selected examples of polypropylene production where the
propylene monomer itself acts as the diluent.

[0008] The effluent discharged from the reactor typically includes the
polymer fluff as well as non-polymer components, such as unreacted olefin
monomer (and comonomer), diluent, inerts, other hydrocarbons, and so
forth. In the case of polyethylene production in liquid phase reactors,
such as loop slurry reactors, the non-polymer components primarily
include diluent, such as isobutane, having a small amount of unreacted
ethylene (e.g., 5 wt. %) and other entrained hydrocarbons. For
polypropylene production, the non-polymer components primarily include
unreacted propylene monomer having a small amount of other entrained
hydrocarbons. The reactor effluent is generally processed, such as by an
effluent treatment system, to separate the non-polymer components from
the polymer fluff. The polymer fluff may then be treated to deactivate
residual catalyst, remove entrained hydrocarbons, dry the polymer, and
pelletize the polymer in an extruder, and so forth, before the polymer is
sent to a customer.

[0009] The non-polymer components, such as the recovered diluent,
unreacted monomer, and other non-polymer components from the effluent
treatment system, may be treated within a fractionation system to
separate most of the recovered diluent from the other non-polymer
components. The recovered diluent may ultimately be returned as purified
or treated feed to the reactor while the other non-polymer components may
be flared or returned to the supplier, such as to an olefin manufacturing
plant or petroleum refinery. Typically, the fractionation system may
employ fractionation columns to separate the diluent from the other
non-polymer components. One or more of the fractionation columns may
employ cold temperatures to facilitate separation of some of the
components, particularly those with lower boiling points than the
diluent. To achieve the cold temperatures, refrigeration systems may be
employed within the fractionation columns. However, it is now recognized
that the refrigeration systems may be costly to operate, install, and/or
maintain.

BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Advantages of the present disclosure may become apparent upon
reading the following detailed description and upon reference to the
drawings in which:

[0011] FIG. 1 is a block flow diagram of a polyolefin manufacturing system
for the production of polyolefins, which includes a membrane separation
system within a fractionation system in accordance with present
embodiments;

[0012] FIG. 2 is a schematic flow diagram of the reactor system of FIG. 1
in accordance with present embodiments;

[0013] FIG. 3 is a schematic flow diagram of the effluent treatment system
and the fractionation system of FIG. 1 in accordance with present
embodiments; and

[0014]FIG. 4 is a schematic flow diagram of another embodiment of the
fractionation system of FIG. 1 in accordance with present embodiments.

DETAILED DESCRIPTION OF SPECIFIC EMBODIMENTS

[0015] One or more specific embodiments of the present disclosure will be
described below. In an effort to provide a concise description of these
embodiments, not all features of an actual implementation are described
in the specification. It should be appreciated that in the development of
any such actual implementation, as in any engineering or design project,
numerous implementation-specific decisions must be made to achieve the
developers' specific goals, such as compliance with system-related and
business-related constraints, which may vary from one implementation to
another. Moreover, it should be appreciated that such a development
effort might be complex and time consuming, but would nevertheless be a
routine undertaking of design, fabrication, and manufacture for those of
ordinary skill having the benefit of this disclosure.

[0016] The present disclosure is directed to polyolefin manufacturing
systems that incorporate fractionation systems with membranes that
separate non-polymer components from the diluent. In general,
fractionation systems may be employed to separate light components or
"lights" and heavy components or "heavies" from the diluent. As used
herein, light components or "lights" may refer to components with lower
boiling points than the diluent employed, and heavy components or
"heavies" may refer to those components with higher boiling points than
the diluent employed. For example, in polyethylene production where
isobutane is the diluent, lights may include unreacted monomer (e.g.,
ethylene), other hydrocarbons (e.g., ethane), and other components (e.g.,
hydrogen and nitrogen), among others, while heavies may include unreacted
comonomer (e.g., 1-butene), oligomers, and other hydrocarbons (e.g.,
hexane), among others.

[0017] In general, fractionation columns may be employed to separate the
non-polymer components from the diluent. For example, the fractionation
systems disclosed herein may employ one or more fractionation columns to
separate the heavy components from the diluent. However, to separate the
light components from the diluent, the fractionation systems disclosed
herein may employ one or more hydrocarbon absorption membranes instead of
fractionation columns. Indeed, it is now recognize that the use of such
membranes for lights separation may reduce operating, capital, and/or
maintenance costs when compared to the costs incurred when using
traditional fractionation columns for lights separation.

[0018] In general, fractionation columns may separate components based on
differences in boiling points. However, light components may have very
low boiling points. Accordingly, a lights fractionation column typically
employs a refrigeration system to achieve temperatures low enough to
facilitate separation of the light components. The refrigeration system
may include rotating equipment and associated piping, which may increase
maintenance, capital, and/or operating costs relative to a process that
does not include a refrigeration system. Further, additional expenses may
be incurred with higher throughputs because the operating efficiency of
the refrigeration system may be affected by load variations in the
fractionation system. Moreover, inclusion of extra equipment may be
required by aspects related to operation of the refrigeration system,
which may increase costs and/or complexity. For example, a dryer may be
included upstream of a lights fractionation column to remove water, which
may freeze at the low temperatures produced by the refrigeration system.

[0019] In contrast to the traditional use of fractionation columns for
lights separation, the hydrocarbon absorption membranes may separate the
light components based on solubility, size, or both, without using a
refrigeration system. Accordingly, it is now recognized that capital,
maintenance, and/or operating costs may be reduced relative to
traditional separation system by eliminating the need for a refrigeration
system. Further, the operating efficiency of the hydrocarbon absorption
membranes may not be affected by load variations. Moreover, the
fractionation systems employing hydrocarbon absorption membranes may
provide increased diluent recovery relative to fractionation systems not
employing hydrocarbon absorption membranes. For example, according to
certain embodiments, it is believed that the fractionation systems
disclosed herein may provide diluent recovery of at least approximately
99.99 percent of the diluent in the reactor effluent. The fractionation
systems disclosed herein may be particularly well suited to polyolefin
manufacturing processes employing loop slurry reactors. However, the
fractionation system disclosed herein also may be employed in polyolefin
manufacturing processes that utilize other types of liquid phase reactors
as well.

[0021] According to certain embodiments, ethylene feedstock may be
supplied by one or more pipelines at approximately 55-100 bar (800-1450
pounds per square inch gauge (psig)) at approximately 7-18° C.
(45-65° F.). In another example, hydrogen feedstock may be
supplied by pipeline at approximately 62-69 bar (900-1000 psig) at
approximately 32-43° C. (90-110° F.). As may be
appreciated, the types, combinations, and/or supply methods of the
feedstocks may vary depending on factors, such as production capacity,
location, design criteria, and the desired type of polyolefin product,
among others.

[0022] The suppliers 12 may provide the feedstocks 14 to a reactor feed
system 16 where the feedstocks 14 may be stored, such as in monomer
storage and feed tanks, diluent vessels, catalyst tanks, co-catalyst
cylinders and tanks, and so forth. Within the feed system 16, the
feedstocks 14 may be treated and/or processed to produce feed streams 18
for a reactor system 20. For example, the feed system 16 may include
treatment beds (e.g., molecular sieve beds, aluminum packing, etc.) that
remove catalyst poisons from the feedstocks 14. According to certain
embodiments, the catalyst poisons may include water, oxygen, carbon
monoxide, carbon dioxide, and organic compounds containing sulfur,
oxygen, or halogens, among others.

[0023] The feed system 16 also may prepare or condition the feedstocks 14
for addition to polymerization reactors in the reactor system 20. For
example, a catalyst may be activated and then mixed with diluent (e.g.,
isobutane or hexane) or mineral oil in catalyst preparation tanks.
Further, the feed system 16 may meter and control the addition rate of
the feedstocks 14 into the reactor system 20 to maintain the desired
reactor stability and/or to achieve the desired polyolefin properties or
production rate.

[0024] In addition to processing the feedstocks 14, the feed system 16 may
store, treat, and meter recovered reactor effluent for recycle to the
reactor system 20. For example, diluent may be recovered from the reactor
effluent and recycled to the reactor system 20. According to certain
embodiments, only a relatively small amount of fresh make-up diluent may
be utilized in the feedstocks 14, while a majority of the diluent fed to
the reactor system 20 may be recovered from the reactor effluent. In
another example, catalyst may be recovered from the reactor effluent and
recycled to the reactor system 20.

[0025] In summary, the feedstocks 14 and the recovered reactor effluent
are processed in the feed system 16 and fed as feed streams 18 (e.g.,
streams of monomer, comonomer, diluent, catalysts, co-catalysts,
hydrogen, additives, or combinations thereof) to the reactor system 20.
The feed streams 18 may be liquid, gaseous, or a supercritical fluid,
depending on the type of reactor or reactors within the reactor system
20.

[0026] The reactor system 20 may include one or more polymerization
reactors, such as liquid-phase reactors, gas-phase reactors, or a
combination thereof. Multiple reactors may be arranged in series, in
parallel, or in any other suitable combination or configuration. Within
the polymerization reactors, one or more olefin monomers and/or
comonomers may be polymerized to form a product containing polymer
particulates, typically called fluff or granules. According to certain
embodiments, the olefin monomers and comonomers may include 1-olefins
having up to 10 carbon atoms per molecule and typically no branching
nearer the double bond than the 4-position. For example, the monomers and
comonomers may include ethylene, propylene, butene, 1-pentene, 1-hexene,
1-octene, and 1-decene. The fluff may possess one or more melt, physical,
rheological, and/or mechanical properties of interest, such as density,
melt index (MI), melt flow rate (MFR), copolymer or comonomer content,
modulus, and crystallinity. The reaction conditions, such as temperature,
pressure, flow rate, mechanical agitation, product takeoff, component
concentrations, polymer production rate, and so forth, may be selected to
achieve the desired fluff properties.

[0027] The catalyst within the feed stream 18 may facilitate
polymerization of the monomer within the reactor vessels. According to
certain embodiments, the catalyst may include particles suspended in the
fluid medium within the reactor. In general, Ziegler catalysts,
Ziegler-Natta catalysts, metallocenes, and other well-known polyolefin
catalysts, as well as co-catalysts, may be used. According to certain
embodiments, the catalyst may be a chromium oxide catalyst containing
hexavalent chromium on a silica support.

[0028] The diluent within the feed stream 18 may be used to suspend the
catalyst particles and the formed polymer particles within the reactor
vessels. According to certain embodiments, the diluent may be an inert
hydrocarbon that is liquid at reaction conditions, such as isobutane,
propane, n-butane, n-pentane, i-pentane, neopentane, n-hexane,
cyclohexane, cyclopentane, methylcyclopentane, or ethylcyclohexane, among
others.

[0029] One or more motive devices may be present within the reactor
vessels in the reactor system 20. For example, within a liquid-phase
reactor, such as a loop slurry reactor, an impeller may create a
turbulent mixing zone within the fluid medium. The impeller may be driven
by a motor to propel the fluid medium as well as any catalyst, polymer
particles, or other solid particulates suspended within the fluid medium,
through the closed loop of the reactor.

[0030] The formed polymer particles, as well as non-polymer components,
such as the diluent, unreacted monomer/comonomer, and residual catalyst,
may exit the reactor system 20 as effluent 22. After leaving the reactor
system 20, the effluent 22 may be subsequently processed, such as by an
effluent treatment system 24, to separate the non-polymer components 26
(e.g., diluent, unreacted monomer, and comonomer) from the formed polymer
particles. After separation, the formed polymer particles may exit the
effluent treatment system 24 as polymer fluff 28.

[0031] The non-polymer components 26 may be processed, for example, by a
fractionation system 30, to remove undesirable light and heavy components
and produce fractionated product streams 32. The fractionated product
streams 32 may then be returned to the reactor system 20 via the feed
system 16. In addition, some or all of the non-polymer components 26 may
bypass the fractionation system 30 to be recycled more directly to the
feed system 16 as non-fractionated product streams 34. Additionally, in
some embodiments, the fractionation system 30 may perform fractionation
of the feedstocks 14 before introduction into the feed system 16, such
that any one or combination of polymerization components may be
controllably fed into the reactor system 20. For example, the
fractionation system 30 may separate monomer components from diluent
components to allow monomer and diluent components to be fed separately
into the reactor system 20.

[0032] The polymer fluff 28 may be further processed within the effluent
treatment system 24 and/or in an extrusion/loadout system 36. Although
not illustrated, polymer granules and/or active residual catalyst in the
effluent treatment system 24 may be returned to the reactor system 20 for
further polymerization, such as in a different type of reactor or under
different reaction conditions.

[0033] In the extrusion/loadout system 36, the polymer fluff 28 is
typically extruded to produce polymer pellets 38 with the desired
mechanical, physical, and melt characteristics. According to certain
embodiments, extruder feed, including additives, such as UV inhibitors
and peroxides, may be added to the polymer fluff 28 to impart desired
characteristics to the extruded polymer pellets 38. An
extruder/pelletizer within the extrusion/loadout system 36 receives the
extruder feed, containing the polymer fluff 28 and whatever additives
have been added. The extruder/pelletizer heats and melts the extruder
feed, which then may be extruded (e.g., via a twin screw extruder)
through a pelletizer die of the extrusion/loadout system 36 under
pressure to form polyolefin pellets 38. The pellets 38 may be cooled in a
water system disposed at or near the discharge of the
extruder/pelletizer.

[0034] In general, the polyolefin pellets 38 may then be transported to a
product load-out area where the pellets may be stored, blended with other
pellets, and/or loaded into railcars, trucks, bags, and so forth, for
distribution to customers 40. In the case of polyethylene, the polyolefin
pellets 38 may include low density polyethylene (LDPE), linear low
density polyethylene (LLDPE), medium density polyethylene (MDPE), high
density polyethylene (HDPE), and enhanced polyethylene. The various types
and grades of polyethylene pellets 38 may be marketed, for example, under
the brand names Marlex® polyethylene or MarFlex® polyethylene of
Chevron-Phillips Chemical Company, LP, of The Woodlands, Tex., USA.

[0035] The polymerization and effluent treatment portions of the
polyolefin manufacturing process 10 may be called the "wet end" 42 or
"reaction side" of the process 10, while the extrusion/loadout portion of
the polyolefin process 10 may be called the "dry end" 44 or "finishing
side" of the polyolefin process 10.

[0036] The produced polyolefin (e.g., polyethylene) pellets 38 may be used
in the manufacture of a variety of products, components, household items
and other items, including adhesives (e.g., hot-melt adhesive
applications), electrical wire and cable, agricultural films, shrink
film, stretch film, food packaging films, flexible food packaging, milk
containers, frozen-food packaging, trash and can liners, grocery bags,
heavy-duty sacks, plastic bottles, safety equipment, coatings, toys and
an array of containers and plastic products. Ultimately, the products and
components formed from the polyolefin pellets 38 may be further processed
and assembled for distribution and sale to the consumer. For example, a
polyethylene milk bottle may be filled with milk for distribution to the
consumer, or the fuel tank may be assembled into an automobile for
distribution and sale to the consumer.

[0037] To form end-products or components from the polyolefin pellets 38,
the polyolefin pellets 38 are generally subjected to further processing,
such as blow molding, injection molding, rotational molding, blown film,
cast film, extrusion (e.g., sheet extrusion, pipe and corrugated
extrusion, coating/lamination extrusion, etc.), and so on. Blow molding
is a process used for producing hollow plastic parts. The process
typically employs blow molding equipment, such as reciprocating screw
machines, accumulator head machines, and so on. The blow molding process
may be tailored to meet the customer's needs, and to manufacture products
ranging from the plastic milk bottles to the automotive fuel tanks
mentioned above. Similarly, in injection molding, products and components
may be molded for a wide range of applications, including containers,
food and chemical packaging, toys, automotive, crates, caps and closures,
to name a few.

[0038] Extrusion processes may also be used. Polyethylene pipe, for
example, may be extruded from polyethylene pellet resins and used in an
assortment of applications due to its chemical resistance, relative ease
of installation, durability and cost advantages, and the like. Indeed,
plastic polyethylene piping has achieved significant use for water mains,
gas distribution, storm and sanitary sewers, interior plumbing,
electrical conduits, power, and communications ducts, chilled water
piping, well casing, to name a few applications. In particular,
high-density polyethylene (HDPE), which generally constitutes the largest
volume of the polyolefin group of plastics used for pipe, is tough,
abrasion-resistant and flexible (even at subfreezing temperatures).
Furthermore, HDPE pipe may be used in small diameter tubing and in pipe
up to more than 8 feet in diameter. In general, polyethylene pellets
(resins) may be supplied for the pressure piping markets, such as in
natural gas distribution, and for the non-pressure piping markets, such
as for conduit and corrugated piping.

[0039] Rotational molding is a high-temperature, low-pressure process used
to form hollow parts through the application of heat to biaxially-rotated
molds. Polyethylene pellet resins generally applicable in this process
are those resins that flow together in the absence of pressure when
melted to form a bubble-free part. Polyolefin pellets 38, such as certain
Marlex® HDPE and MDPE resins, offer such flow characteristics, as
well as a wide processing window. Furthermore, these polyethylene resins
suitable for rotational molding may exhibit desirable low-temperature
impact strength, good load-bearing properties, and good ultraviolet (UV)
stability. Accordingly, applications for rotationally-molded Marlex®
resins include agricultural tanks, industrial chemical tanks, potable
water storage tanks, industrial waste containers, recreational equipment,
marine products, plus many more.

[0040] Sheet extrusion is a technique for making flat plastic sheets from
a variety of polyolefin pellet resins. The relatively thin gauge sheets
are generally thermoformed into packaging applications such as drink
cups, deli containers, produce trays, baby wipe containers and margarine
tubs. Other markets for sheet extrusion of polyolefin include those that
utilize relatively thicker sheets for industrial and recreational
applications, such as truck bed liners, pallets, automotive dunnage,
playground equipment, and boats. A third use for extruded sheet, for
example, is in geomembranes, where flat-sheet polyethylene material is
welded into large containment systems for mining applications and
municipal waste disposal.

[0041] The blown film process is a relatively diverse conversion system
used for polyethylene. The American Society for Testing and Materials
(ASTM) defines films as less than 0.254 millimeter (10 mils) in
thickness. However, the blown film process can produce materials as thick
as 0.5 millimeter (20 mils), and higher. Furthermore, blow molding in
conjunction with monolayer and/or multilayer coextrusion technologies
provide the groundwork for several applications. Advantageous properties
of the blow molding products may include clarity, strength, tearability,
optical properties, and toughness, to name a few. Applications may
include food and retail packaging, industrial packaging, and
non-packaging applications, such as agricultural films, hygiene film, and
so forth.

[0042] The cast film process may differ from the blown film process
through the fast quench and virtual unidirectional orientation
capabilities. These characteristics allow a cast film line, for example,
to operate at higher production rates while producing beneficial optics.
Applications in food and retail packaging take advantage of these
strengths. Finally, the polyolefin pellets 38 may also be supplied for
the extrusion coating and lamination industry.

[0043] FIG. 2 depicts an embodiment of the reactor system 20 shown in FIG.
1. As discussed above with respect to FIG. 1, the reactor system 20 may
include one or more polymerization reactors of the same or different
types. Furthermore, in multiple reactor systems, the reactors may be
arranged in series or in parallel. To facilitate explanation, the
following examples are limited in scope to specific reactor types
believed to be familiar to those skilled in the art and to single
reactors or simple combinations. To one of ordinary skill in the art
using this disclosure, however, the present techniques are simply and
easily applicable to more complex reactor arrangements, such as those
involving additional reactors, different reactor types, and/or
alternative ordering of the reactors or reactor types. Such arrangements
are considered to be well within the scope of the present techniques.

[0044] The reactor system 20 includes a liquid phase reactor, such as a
loop slurry reactor 50, generally composed of segments of pipe connected
by smooth bends or elbows. For simplicity, FIG. 2 depicts a loop slurry
reactor 50. However, in other embodiments, the present techniques may be
similarly applicable to other types of liquid phase reactors. For
example, the reactor system 20 may include other types of liquid phase
reactors, such as autoclaves, boiling liquid-pool reactors, or vertical
and/or horizontal loop slurry reactors, among others.

[0045] As shown, the loop slurry reactor 50 includes four vertical pipe
legs formed integrally with horizontal pipe legs (or curved connecting
members). According to certain embodiments, the pipe legs may be
approximately 24 inches in diameter and approximately 200 feet in length,
connected by pipe elbows at the top and bottom of the legs. However, in
other embodiments, the diameter, length, and number and/or types of legs
may vary. For example, in other embodiments, the loop slurry reactor 50
may include as many as eight to sixteen vertical pipe legs. Further, in
other embodiments, more than sixteen vertical pipe legs may be included.
In another example, the horizontal members may be eliminated while the
vertical legs are connected through curved connecting members. Further,
in another example, the pipe legs may be arranged horizontally without
vertical pipe legs. In the illustrated embodiment, each leg includes a
reactor jacket 52 that may remove heat from the exothermic polymerization
via circulation of a cooling medium, such as treated water, through the
reactor jacket 52.

[0046] In general, the loop slurry reactor 50 may be used to carry out
polyolefin polymerization under slurry conditions in which insoluble
particles of polyolefin are formed in a fluid medium and are suspended as
slurry within the loop slurry reactor 50. A motive device, such as pump
54, circulates the fluid slurry in the reactor 50. According to certain
embodiments, the pump 54 may be an in-line axial flow pump with a pump
impeller disposed within the interior of the loop slurry reactor 50 to
create a turbulent mixing zone within the fluid medium. The impeller also
may assist in propelling the fluid medium through the closed loop of the
reactor at sufficient speed to keep solid particulates, such as the
catalyst and the polyolefin product, suspended within the fluid medium.
The impeller may be driven by a motor 56 or other motive force.

[0047] The fluid medium, which may be supplied to the reactor 50 by the
feed streams 18, may include olefin monomers and comonomers, diluent,
co-catalysts (e.g., alkyls, triethylboron, methyl aluminoxane, etc.),
molecular weight control agents (e.g., hydrogen), and any other desired
co-reactants or additives. For example, feed stream 18A may supply the
olefin monomers, olefin comonomers, and diluent components to the reactor
50 via inlets and conduits. Feed stream 18B may supply the catalyst along
with a diluent carrier to the reactor 50 via inlets and conduits. For
example, the catalyst may include particles suspended in the diluent
carrier. The feed stream conduits may be connected to the reactor 50 by
flanges, welds, or other suitable types of attachments.

[0048] The reaction conditions, such as temperature, pressure, and
reactant concentrations, are regulated to facilitate the desired
properties and production rate of the polyolefin in the reactor, to
control stability of the reactor, and the like. Temperature is typically
maintained below the level at which the polymer product would go into
solution, swell, soften, or become sticky. As indicated, due to the
exothermic nature of the polymerization reaction, a cooling fluid may be
circulated through jackets 52 around portions of the loop slurry reactor
50 to remove excess heat, thereby maintaining the temperature within the
desired range, generally between 150-250° F. (65-121° C.).
Pressure also may be regulated within a desired pressure range, such as
7-55 bar (100-800 psig), with a range of 31-48 bar (450-700 psig) being
typical.

[0049] As the polymerization reaction proceeds within the reactor 50, the
monomer (e.g., ethylene) and comonomers (e.g., 1-hexene) polymerize to
form polyolefin (e.g., polyethylene) polymers that are substantially
insoluble in the fluid medium at the reaction temperature, thereby
forming a slurry of solid particulates within the medium. These solid
polyolefin particulates may be removed from the reactor 50 via one or
more settling legs, continuous take-offs, or other suitable withdrawal
systems, to produce the effluent 22. The effluent 22 may then be
processed, for example, within the effluent treatment system 24 (FIG. 1)
and the extrusion/loadout system 36 (FIG. 1), to extract and purify the
polyolefin particles formed within the reactor 50.

[0050] FIG. 3 depicts an embodiment of the effluent treatment system 24
and the fractionation system 30 shown in FIG. 1. The effluent 22 from the
reactor system 20 (FIG. 2) may be directed to the effluent treatment
system 24 where the effluent 22 may flow through an in-line flash heater
62 and into a separation vessel 64. The in-line flash heater 62 may be a
surrounding conduit that uses a heating medium, such as steam or steam
condensate, to provide indirect heating to the effluent 22 prior to
introduction of the effluent 22 into the separation vessel 64. According
to certain embodiments, the in-line flash heater 62 may vaporize at least
a portion of the diluent within the effluent 22. Moreover, in certain
embodiments, the in-line flash heater 62 may be designed to vaporize
(i.e. "flash") essentially all of the liquid diluent so that the effluent
22 entering the separation vessel 64 includes solids and vapors, without
much liquid. Further, although not shown, water or other catalysts
poisons may be injected into the effluent 22 upstream of the separation
vessel 64 to deactivate residual catalyst included in the effluent 22.
The injected catalyst poisons may be later removed in the recycle
fractionation process. For example, the catalyst poisons may be removed
within the fractionation system 30.

[0051] The separation vessel 64 may include a settling drum, a high
efficiency cyclone, a flash gas separator, or combinations thereof, among
others. In the separation vessel 64, most of the non-solid components,
such as diluent, unreacted monomer, unreacted comonomer, lights, and
heavies, rise toward a top portion of the separation vessel 64 and exit
the separation vessel 64 in a flash gas stream 66. As noted above, light
components or "lights" may be defined as components with lower boiling
points than the diluent employed while heavy components or "heavies" may
be defined as those components having higher boiling points than the
diluent. For example, in embodiments employing isobutane as the diluent,
lights may include components such as ethane, propane, or nitrogen, among
others, while heavies may include components such as hexane and
oligomers, among others.

[0052] According to certain embodiments, the flash gas stream 66 may
include primarily diluent. For example, in polyolefin production, the
flash gas stream 66 may include primarily isobutane. The flash gas stream
66 also may include most of the unreacted monomer (e.g., ethylene) and
other light components, as well as unreacted comonomer (e.g., 1-hexene,
butene, 1-pentene, 1-octene, and 1-decene) and other heavy components
(e.g., hexane and oligomers). According to certain embodiments designed
to produce polyethylene, the flash gas 66 may include approximately 94
weight percent isobutane, 5 weight percent ethylene, and 1 weight percent
of other components. A level or volume of fluff may be maintained in the
separation vessel 64 to provide additional residence time for the fluff
in the separation vessel 64. The increased residence time may facilitate
separation of the non-polymeric material from the polymer fluff
particles.

[0053] The flash gas stream 66 may be directed to a solids removal system
68 where entrained polymer solids 70 may be removed and returned to the
separation vessel 64. The solids removal system 68 may include equipment,
such as cyclones, bag filters, guard filters, and the like, for removing
the entrained polymer solids 70 from the flash gas 66. Further, in other
embodiments, the removed polymer solids 70 may be directed to downstream
equipment, such as a purge column 72, discussed further below. The flash
gas stream 66 exiting the solids removal system 68 may then be directed
to a recycle tank 74. In other embodiments, the flash gas stream 66 may
be directed through additional equipment, such as a de-oxygenation bed
and/or a condenser, among others, prior to entering the recycle tank 74.
Further, in certain embodiments, the solids removal system 68 may be
omitted.

[0054] Within the recycle tank 74 some or most of the diluent within the
flash gas stream 66 may be condensed to produce the non-fractionated
product streams 34 that are returned to the reactor system 20 through the
feed system 16, as shown in FIG. 1. The non-fractionated product streams
34 exiting the recycle tank 74 are directly recycled to the reactor
system 20 without passing through the fractionation system 30. As
discussed above with respect to FIG. 1, the non-polymeric material 26
exiting the effluent treatment system 24 may be returned to the reactor
system 20 through both the non-fractionated product streams 34 and the
fractionated product streams 32. According to certain embodiments, at
least approximately 50-99 percent of the non-polymeric material 26 may be
recycled, recovered, or fractionated within the manufacturing system 10.
In general, most of the material exiting the effluent treatment system 24
may be directly recycled as non-fractionated product streams 34, with a
relatively small portion of the material exiting the effluent treatment
system 24 being directed as one or more slip streams to the fractionation
system 30. The relatively small portion of material entering the
fractionation system 30 may allow equipment within the fractionation
system 30 to be reduced in size.

[0055] Within the separation vessel 64, the solid components, which are
mostly polymer fluff, may fall to a bottom portion of the separation
vessel 64 where the solid components may be withdrawn as a solids
discharge 76 and directed to the purge column 72. The solids discharge 76
also may include a small amount of entrained diluent and/or entrained
monomer.

[0056] Although not shown, the solids discharge 76 may flow through one or
more valve configurations that allow the solids discharge 76 to flow
downward to the purge column 72 while reducing the potential for vapor to
flow between the purge column 72 and the separation vessel 64. For
example, the solids discharge 76 may be directed through equipment, such
as one or more rotary or cycling valves, a single Vee-Ball® control
valve, fluff surge tanks, or a relatively small fluff chamber, among
others, prior to entering the purge column 72. According to certain
embodiments, a level of solid components may be maintained in the
separation vessel 64, for example, via a level control valve, which may
increase the residence time of the solid components in the separation
vessel 64, thereby promoting improved separation of the solid and
non-solid components. Further, certain configurations may provide for
continuous fluff discharge from the separation vessel 64, which may
eliminate one or more cycling valves.

[0057] Within the purge column 72, purge gas may be employed to remove
residual hydrocarbons, such as entrained diluent, heavies, and lights,
from the solid components. For example, nitrogen may be fed to the purge
column 72 to remove residual hydrocarbons in a residual hydrocarbon
stream 78 that may exit the purge column 72 as overhead discharge.
Removal of the residual hydrocarbons may yield the polymer fluff 28,
which may be removed from the purge column 72 and directed to the
extrusion/loadout system 36 for further processing as described above
with respect to FIG. 1.

[0058] The residual hydrocarbon stream 78, containing the nitrogen purge
gas and the extracted residual hydrocarbons, may be sent through a
separation unit 80. According to certain embodiments, the separation unit
80 may include a membrane recovery unit, pressure swing adsorption unit,
or a refrigeration unit, among others. In the art, the separation unit 80
may be known as a Diluent Recovery Unit (DRU). Further, in some
embodiments, such as the manufacturing system 10 (FIG. 1) employing
isobutane diluent, the separation unit 80 may be an Isobutane Nitrogen
Recovery Unit (INRU).

[0059] Within the separation unit 80, the purge gas may be separated from
the extracted residual hydrocarbons. Accordingly, the separation unit 80
may produce a purge gas stream 82 and a stream 84 that contains the
residual hydrocarbons. The purge gas stream 82 may be directed to the
purge column 72 to extract more residual hydrocarbons from the polymer
fluff. Further, although not shown, fresh purge gas, such as nitrogen,
may be added with the recovered purge gas 82 to make up for purge gas
losses within the purge column 72.

[0060] The stream 84 may be separated into two streams 86 and 88, each
containing diluent, heavies, and lights. According to certain
embodiments, the streams 86 and 88 may primarily contain diluent and
heavies. However, the streams 86 and 88 also may contain some lights. The
stream 86 may be directed to the recycle tank 74. According to certain
embodiments, the recycle tank 74 may be designed to function as a
vapor-liquid separation drum that flashes, or otherwise separates, the
lights from the liquid diluent and heavies. For example, the lights may
collect in a top portion of the recycle tank 74 and may exit the recycle
tank 74 in a vapor stream 90 that enters the fractionation system 30. The
stream 88 also may be directed to the fractionation system 30.
Specifically, the stream 88 may be directed to a heavies fractionation
column 92 within the fractionation system 30.

[0061] As may be appreciated, the effluent treatment system 24 is provided
by way of example only, and it not intended to be limiting. For example,
the effluent treatment system 24 may employ other equipment and/or
configurations. According to certain embodiments, the purge column 72 may
be replaced by another reactor, such as a gas phase reactor. In other
embodiments, the solids discharge 76 from the separation vessel 64 may be
directed through a low-pressure flash chamber prior to entering the purge
column 72. Further, the purge column 72 may be combined with equipment,
such as an extruder feed tank, located in the extrusion/loadout system
36.

[0062] The fractionation system 30 may receive and process the residual
hydrocarbons exiting the effluent treatment system 24. For example, the
fractionation system 30 may receive the residual hydrocarbons through the
vapor stream 90 exiting the recycle tank 74 and through the stream 88
exiting the separation unit 80. As noted above, the residual hydrocarbons
may include diluent, lights, such as unreacted monomer (e.g., ethylene),
ethane, and inerts, among others, and heavies, such as unreacted
comonomer (e.g., 1-hexane), oligomers, hexane, and the like. In general,
the fractionation system 30 may be designed to remove heavies and lights
from the diluent to impede the build up of heavies and lights within
manufacturing system 10 (FIG. 1). The fractionation system 30 may include
the heavies fractionation column 92, which may be designed to remove
heavies from the diluent, and a membrane system 94, which may be designed
to remove lights from the diluent.

[0063] To prevent the build up of heavies within the manufacturing system
10 (FIG. 1), a portion or all of the extracted hydrocarbons exiting the
separation unit 80 may be directed to the heavies fractionation column 92
through the stream 88. In general, the heavies fractionation column 92
may use distillation to separate the hydrocarbon components based on
their different boiling points, for example, by preferentially boiling
the more volatile components out of the stream 88. According to certain
embodiments, the heavies fractionation column 92 may operate at a
pressure of approximately 9-12 bar (125-175 psig) and a temperature of
approximately 60-177° C. (140-350° F.). However, in other
embodiments, the temperature and pressure ranges may vary.

[0064] Within the heavies fractionation column 92, liquid and vapor may
typically flow counter-currently, contacting each other through internals
96. The internals 96 may include trays, plates, and packing, among
others, and may be used to create stages that provide improved contact
between the liquid and vapor flows, thereby, promoting separation. The
heavies may generally condense within the column and flow to a bottom
portion of the column 92. The heavies may then exit the heavies
fractionation column 92 in a bottoms discharge 98, which may be directed
to a flare, to an incinerator, or to a tank for disposal.

[0065] The bottoms discharge 98 may generally include the least volatile
components, for example, components with a boiling point that is less
than the boiling point of the diluent. According to certain embodiments
employing the diluent isobutane, the heavies may include hexane, hexene,
and oligomers, among others. A portion 100 of the bottoms discharge 98
may be directed through a reboiler 102 where a heating medium, such as
steam or steam condensate, may be used to vaporize some of the portion
100. The vapor exiting the reboiler 102 may be returned to the heavies
fractionation column 92 to facilitate further separation of the
components within the heavies fractionation column 92. For example, the
portion 100 exiting the reboiler 102 may be directed to a bottom portion
of the column where the vapor may flow up the heavies fractionation
column 92 in countercurrent flow with the liquid flowing down the heavies
fractionation column 92.

[0066] As the stream 88 flows down the heavies fractionation column 92,
the more volatile components may vaporize and collect within a top
portion of the heavies fractionation column 92. The more volatile
components may then exit the heavies fractionation column 92 as an
overhead discharge stream 104 that may include primarily diluent, such as
isobutane, and lights, such as ethylene and ethane, hydrogen, and
nitrogen, among others. In general, the heavies fractionation column 92
may separate components based on their boiling points to produce the
bottoms discharge 98, which is concentrated with the heavies, and the
overhead discharge 104, which is concentrated with the lights and the
diluent.

[0067] The overhead discharge stream 104 may be directed through a
condenser 106 where a portion 108 of the overhead discharge stream 104
may be condensed and used as reflux for the heavies fractionation column
92. In particular, the condensed portion 108 may be returned to an upper
section of the heavies fractionation column 92 via a pump 110. In certain
embodiments the condenser 106 may include a shell and tube heat exchanger
or other type of heat exchanger. Further, an accumulator may be included
with the condenser 106 to promote separation of the condensed liquid from
the vapor.

[0068] The vaporized portion of the overhead discharge stream 104 may exit
the condenser 106 as a vapor stream 112 that may be combined with the
vapor stream 90 exiting the recycle tank 74 to form a stream 111 that is
directed to the membrane system 94. Because most of the heavies are
removed within the heavies fractionation column 92 and/or within the
recycle tank 74, the vapor streams 90 and 112 may contain primarily
diluent and lights. However, some heavies that may have a boiling point
slightly higher than the diluent, such a comonomer (e.g., 1-butene), may
also be included within the vapor streams 90 and 112. For example, in
certain embodiments, the vapor streams 90 and 112 may contain
approximately 5-20 percent by weight of 1-butene.

[0069] The vapor streams 90 and 112 may be directed to the membrane
separation system 94 where the lights may be separated. As shown, the
vapor streams 90 and 112 are combined into a single feed stream 111 prior
to entering the membrane separation system 94. However, in other
embodiments, the vapor streams 90 and 112 may enter the membrane
separation system 94 as separate streams. Further, in certain
embodiments, the feed stream 111 may be directed through a compressor 113
prior to entering the membrane separation system 94. However, in other
embodiments, the compressor 113 may be omitted or may be part of the
membrane separation system 94.

[0070] The membrane separation system 94 may include one or more membrane
modules 114 and 116 designed to separate lights and heavies. The membrane
modules 114 and 116 may include hydrocarbon absorption membranes 115 and
119 designed to separate hydrocarbons and other components based on
solubility, molecular size, or both. In certain embodiments where
isobutane is employed as the diluent, the hydrocarbon absorption
membranes may be designed to separate lights, such as ethylene, ethane,
and nitrogen, among others, from the diluent isobutane. The membrane
modules 114 and 116 may include any suitable type of gas separation
membrane modules, such as spiral wound or hollow-fiber membrane modules,
among others. According to certain embodiments, the membrane modules 114
and 116 may include VaporSep® membrane modules commercially available
from Membrane Technology and Research, Inc. of Menlo Park, Calif.

[0071] Each membrane module 114 and 116 may include gas separation
membranes 115 and 119 with one or more layers designed to promote
separation of the diluent and lights. For example, the membranes 115 and
119 may include a nonwoven fabric layer designed to serve as a substrate,
a solvent resistant microporous support layer designed to provide
mechanical support, and a nonporous selective layer that performs the
separation. In certain embodiments, the microporous support layer and the
nonporous selective layer may be cross-linked to one another.

[0072] As shown in FIG. 3, the membranes 115 and 119 may be designed to
allow larger hydrocarbon molecules to permeate through the membranes 115
and 119 while retaining smaller hydrocarbon molecules and other smaller
molecules on the other side of the membrane 115 and 119. For example,
where the membranes 115 and 119 are designed to separate molecules by
solubility, the membranes 115 and 119 may include a selective layer of a
rubbery polymer, such as silicone rubber, that allows larger hydrocarbon
molecules to permeate the membranes 115 and 119 based on their higher
solubility in the membrane polymer. In another example, where the
membranes 115 and 119 are designed to separate molecules by size, the
membranes 115 and 119 may include a selective layer that separates the
diluent from the lights based on different diffusion rates. According to
certain embodiments where the diluent is isobutane, the membranes 115 and
119 may be designed to allow hydrocarbons having four or more carbons to
permeate the membranes 115 and 119 while retaining hydrocarbons with
three or fewer carbon atoms as well as other smaller components.

[0073] The feed stream 111, which, as noted above, contains primarily
diluent and lights, may enter the membrane separation system 94 and flow
through the first membrane module 114. Within the first membrane module
114, the diluent, which has relatively larger hydrocarbon molecules than
the lights, may permeate the membrane 115 and exit the first membrane
module 114 in a diluent enriched steam 117. The diluent enriched stream
117 contains primarily diluent; however, small amounts of entrained
heavies and lights may also be present. According to certain embodiments,
the diluent enriched stream 117 may contain at least 50, 60, 70, 80, or
90 percent by weight of diluent. The lights, which have relatively
smaller hydrocarbon molecules, may be retained by the membrane 115 and
may exit the membrane module 114 in a lights enriched stream 118. The
lights enriched stream 118 may contain primarily lights; however, small
amounts of entrained diluent and heavies may also be present. According
to certain embodiments, the lights enriched stream 118 may contain at
least 40, 50, 60, 70, 80, or 90 percent by weight of lights. In certain
embodiments, the lights enriched stream 118 may flow through one or more
valves 120 which may be adjusted to regulate the driving force across the
membrane module 114.

[0074] The lights enriched stream 118 may then enter the second membrane
module 116 where some or all of the entrained diluent may be removed.
Specifically, the diluent may permeate the membrane 119 and may exit the
membrane module 116 in a diluent enriched stream 122, while the lights
may be retained by the membrane 119 and may exit the membrane module 116
in a lights enriched stream 124. In certain embodiments, the lights
enriched stream 124 may flow through one or more valves 126 which may be
adjusted to regulate the driving force across the membrane module 116.

[0075] The lights enriched stream 124 may contain primarily lights and may
be directed to a flare to remove the lights from the manufacturing system
10 (FIG. 1). According to certain embodiments, the lights enriched stream
124 may contain at least 50, 60, 70, 80, or 90 percent by weight of
lights. In embodiments where the diluent is isobutane, the lights
enriched stream 124 may include components such as ethane, inerts, such
as nitrogen, and unreacted monomer, such as ethylene. In certain
embodiments, some or all of the lights enriched stream 124 may be
directed to additional processing systems where some of the lights, such
as the unreacted monomer, may be recovered and provided to a supplier.
For example, where the monomer is ethylene, the lights enriched steam 124
may be directed to an ethylene unit in a polyethylene manufacturing
process.

[0076] The diluent enriched stream 122 may contain primarily diluent and
may be combined with the diluent enriched stream 117 exiting the first
membrane module 114 to form a single diluent enriched stream 128.
According to certain embodiments, the diluent enriched stream 128 may
contain at least 30, 40, 50, 60, 70, 80, or 90 percent by weight of
diluent. The diluent enriched steam 128 may be directed to the separation
unit 80 where the diluent may be further extracted. However, in other
embodiments, the diluent enriched streams 122 and 117 may be provided to
the separation unit 80 as separate streams. Further, in certain
embodiments, a portion 130 of the diluent enriched stream 128 may be
withdrawn and used in catalyst preparations and/or in reactor flushes.

[0077] The membrane separation system 94 may include any number of
membrane modules, such as the membrane modules 114 and 116, as well as
other equipment. For example, at least one, two, or three membrane
modules may be included within the membrane system 94. In certain
embodiments, the membrane system 94 may be provided as a skid that
includes the membrane modules 114 and 116, which may be surrounded by
pressure vessels, and/or may include additional equipment, such as
compressors, pumps, heat exchangers, and vapor-liquid separators, among
others. Further, the membrane separation system 94 may include
instrumentation and control systems. For example, the membrane separation
system 94 may be compatible with a Distributed Control System (DCS) or
with a Programmable Logic Controller (PLC) based control system.
Moreover, in other embodiments, the membrane separation system 94 may be
part of other equipment within the fractionation system 30. For example,
the membrane separation system 94 may be integrated with the heavies
fractionation column 92 as a top portion of the heavies fractionation
column 92.

[0078]FIG. 4 depicts another embodiment of the membrane separation system
94 that may be employed within the fractionation system 30. As shown in
FIG. 4, the membrane separation system 94 includes membrane modules 132
and 134 with membranes 133 and 135 that are designed to retain diluent
rather than allowing the diluent to permeate through the membranes 115
and 119 as shown in FIG. 3. Similar to the membranes 115 and 119
described above with respect to FIG. 3, the membranes 133 and 135 may
separate the lights and the diluent based on molecular size, solubility,
or both. For example, according to certain embodiments, the membranes 133
and 135 may include glassy polymers that allow smaller hydrocarbon
molecules to permeate the membranes 133 and 135 while impeding the
passage of larger hydrocarbon molecules, such as the diluent.

[0079] As described above with respect to FIG. 3, the heavies
fractionation column 92 and the recycle tank 74 may remove heavies from
the streams 88 and 84. The membrane separation system 94 may then receive
a combined feed stream 111 that includes the vapor steams 90 and 112
exiting the recycle tank 74 and the heavies fractionation column 92,
respectively. However, in other embodiments, the vapor streams 90 and 112
may enter the membrane separation system 94 as separate streams. Within
the membrane separation system 94, the feed stream 111 may flow through
the first membrane module 132. The lights may permeate the membrane 133
and may exit the first membrane module 132 in the lights enriched stream
118. The diluent, on the other hand, may be retained within the first
membrane module 132. Further, in certain embodiments, the diluent, as
well as entrained heavies, may be directed back to the recycle tank 74 as
counterflow within the vapor stream 90. In certain embodiments, the
design of the membrane module 132, which allows lights to permeate the
membrane 133 while impeding the passage of diluent and heavies, may
inhibit the flow of entrained heavies into the membrane separation system
94. Further, in certain embodiments, the driving force created by
inhibiting the passage of diluent through the membrane 133 may reduce the
need for a compressor in the vapor stream 90.

[0080] The lights enriched steam 118 exiting the first membrane module 132
may be directed through a compressor 136 that may be designed to compress
the lights enriched stream 118 prior to entry into the second membrane
module 134. Within the second membrane module 134, the lights may
permeate the membrane 135 and exit the membrane module 134 as the lights
enriched stream 124. The lights enriched stream 124 may then be directed
to a flare or to further processing as described above with respect to
FIG. 3. The diluent retained by the membrane 135 may exit the second
membrane module 134 as the diluent enriched stream 122. According to
certain embodiments, the diluent enriched stream 122 may be separated
into the portion 130, which may used for catalyst flushes and the like,
and the diluent enriched stream 128 that may directed to the separation
unit 80.

[0081] As discussed above with respect to FIG. 3, the membrane separation
system 94 may include additional equipment, such as the valves 120 and
126 that may be adjusted to regulate the driving forces across the
membrane modules 132 and 134. Further, in certain embodiments, the
membrane separation system 94 may be provided as a skid or may be
integrated into other equipment within the fractionation system 30.
Moreover, combinations of the membrane modules described herein may be
employed within membrane separation systems. For example, in certain
embodiments, a membrane separation system may use one or more membrane
modules designed to retain diluent, as described with respect to FIG. 4,
in combination with one or more membrane modules designed to retain
lights, as described with respect to FIG. 3.

[0082] While the present disclosure may be susceptible to various
modifications and alternative forms, specific embodiments have been shown
by way of example in the drawings and tables and have been described in
detail herein. However, it should be understood that the embodiments are
not intended to be limited to the particular forms disclosed. Rather, the
disclosure is to cover all modifications, equivalents, and alternatives
falling within the spirit and scope of the disclosure as defined by the
following appended claims. Further, although individual embodiments are
discussed herein, the disclosure is intended to cover all combinations of
these embodiments.